CN102432795B - Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method - Google Patents
Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method Download PDFInfo
- Publication number
- CN102432795B CN102432795B CN 201110251751 CN201110251751A CN102432795B CN 102432795 B CN102432795 B CN 102432795B CN 201110251751 CN201110251751 CN 201110251751 CN 201110251751 A CN201110251751 A CN 201110251751A CN 102432795 B CN102432795 B CN 102432795B
- Authority
- CN
- China
- Prior art keywords
- reaction
- epoxy
- polyurethane modified
- vulcabond
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 C=*O[N+](*(*=*)=C)[O-] Chemical compound C=*O[N+](*(*=*)=C)[O-] 0.000 description 2
- LHGKPFIMRJCMJP-UHFFFAOYSA-N C=N[N-][N+]([NH+]([O-])O[Ar])=C Chemical compound C=N[N-][N+]([NH+]([O-])O[Ar])=C LHGKPFIMRJCMJP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method. The preparation method comprises the following steps of: adding dropwisely acrylic acid hydroxyl ethyl or hydroxypropyl acrylate and dibutyltin dilaurate into diisocyanate under the protection of nitrogen to obtain a diisocyanate semi-adduct after the reaction; performing a ring-opening esterification reaction between an epoxy resin and 5-sulfo-1,2,4-benzenetricarboxylic acid under the action of a catalyst to obtain epoxy 5-sulfo-1,2,4-benzenetricarboxylic acid ester; performing a reaction between the semi-adduct and epoxy 5-sulfo-1,2,4-benzenetricarboxylic acid ester under the action of a catalyst dibutyltin dilaurate at the temperature of 40-50 DEG C until 2274 cm<-1> absorption peak in the infrared spectrum of the mixture completely disappears, and adding triethylamine at room temperature for neutralization, so as to obtain the sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion. By a properly adjusted formula, the product with required performance can be obtained. The product provided by the invention has good stability and excellent film property, and can be used in aqueous UV curing coating and printing ink fields.
Description
Technical field
The present invention relates to a kind of aqueous epoxy emulsion, particularly relate to a kind of water-based UV polyurethane modified epoxy ACRYLIC EMULSION and synthetic method thereof of tool sulfonic acid type.
Background technology
Ultraviolet-curing paint is at first succeeded in developing and is introduced to the market by Bayer A.G, very fast universal on market, and cause the great attention of various countries, twisted process has been experienced in the development of China, as far back as the seventies in 20th century, some scientific research institutions of China and big coating factory develop ultraviolet-curing paint according to limited data.Ultraviolet-curing paint obtains widespread use with advantages such as its curing speed are fast, energy-conservation, production efficiency is high, coating performance is good over nearly more than 30 years.But along with the fast development of ultraviolet-curing paint, some the drawback exposed day by day of himself are come out, influenced it application and popularization, particularly reactive thinner and volatile organic matter to the infringement of human body and the pollution of environment.The aqueous photo-curing system can overcome these disadvantages.UV-curable waterborne coatings combines the advantage of ultraviolet-curing paint and water-borne coatings.On the one hand, it is with water surrogate response thinner, has eliminated that ultraviolet-curing paint uses volatile organic matter (VOC) and the pollution and the irritating drawback that cause; On the other hand, also for water-borne coatings provides a kind of new curing means, this system has following advantage: (1) is thinner with water, can solve the toxicity and the pungency of volatile constituent, and the viscosity of easy regulation system; (2) do not contain volatile organic matter, nonflammable, production safety, product environmental protection; (3) owing to do not contain diluent monomer, can reduce the shrinkage degree of cured film, help improving the adhesivity of filming ground; (4) can use common coating process, as roller coat, showering and spraying, and coating apparatus is easy to clean; (5) before curing, can obtain inviscid dry film, directly place under repair, contact and stacking.Solved the contradiction between hardness of film and the suppleness in addition.
The water-based oligopolymer is the coating material solidified important component part of water-based UV, is filmogen, and the performance of filming is played decisive influence.The water-based oligopolymer that uses mainly contains unsaturated polyester, urethane acrylate, epoxy acrylate etc. at present.From the structural analysis of oligomer molecules, they all contain the C=C unsaturated link(age), as vinyl, acryloxy, methacryloxy, allyl group etc., because the acryloxy curing speed is fast, so become the principal item of all kinds of acrylic resins; Has a certain amount of hydrophilic radical on the molecular chain simultaneously, as carboxyl, amino, ether, sulfonic group, amide group etc.Most water-based oligopolymer mainly is to be hydrophilic radical with the carboxylate salt, and sulfonic acid type water-based oligopolymer still is not a lot.
In various aqueous photo-curing oligopolymer, what water-based epoxy acrylic ester and aqueous polyurethane acrylate were used is two kinds of many resins.Water-based epoxy acrylic ester resin mainly is earlier by vinylformic acid open loop Resins, epoxy, again with MALEIC ANHYDRIDE esterification introducing carboxyl; Aqueous polyurethane acrylate mainly is to introduce carboxylic group by dimethylol propionic acid in reaction process; These all are to be hydrophilic radical with the carboxyl basically, compare with sulfonic group, the carboxyl electronegativity a little less than, formed oligopolymer wetting ability is not as the latter, the storage in later stage is also unstable.
Summary of the invention
The present invention will solve the problems of the technologies described above and be to provide a kind of sulfonic water-based UV polyurethane modified epoxy ACRYLIC EMULSION preparation method that contains, and its product has advantages such as color and luster is good, and stability in storage is good, and film performance is excellent.
In order to achieve the above object, the present invention adopts following technical scheme:
Sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION preparation method comprises following steps:
(1) under nitrogen protection, Hydroxyethyl acrylate (HEA) or Propylene glycol monoacrylate (HPA) and dibutyl tin laurate (DBTDL) are added drop-wise in the vulcabond, keep 40～50 ℃ of temperature of reaction, in the monitoring system-change in concentration of NCO, no longer change up to-NCO concentration, half affixture of vulcabond; Hydroxyethyl acrylate (HEA) or Propylene glycol monoacrylate (HPA) are 1:1～1.05 with the mol ratio of vulcabond; The mass ratio of dibutyl tin laurate and Hydroxyethyl acrylate or Propylene glycol monoacrylate is 0.9～1.1:100,
(2) with mol ratio be Resins, epoxy and the esterification by ring opening reaction under the effect of catalyzer triphenyl phosphorus of three carboxyl Phenylsulfonic acids of 3:1～1:2, at 120～150 ℃ of reaction 3～5h, acid number is reduced to 25 of system initial acid value～75% o'clock stopped reaction, and reaction obtains epoxy three carboxyl benzene sulfonates;
(3) with acetone solution dibutyl tin laurate (DBTDL), be added drop-wise in the mixture of half affixture that is mixed with the vulcabond in the step (1) and the epoxy three carboxyl benzene sulfonates in the step (2), keep 40～50 ℃ of temperature of reaction, 2274cm in the reaction mixture infrared spectra
-1The absorption peak completely dissolve, the mol ratio of half affixture of vulcabond and epoxy three carboxyl benzene sulfonates is 1:1～3:1; The mass ratio of dibutyl tin laurate and epoxy three carboxyl benzene sulfonates is 0.5～1.0:100;
(4) add triethylamine (TEA), at room temperature carry out neutralization reaction 0.5～1.0h, add water-dispersion and can obtain sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION, the mol ratio of triethylamine and three carboxyl benzene sulfonates is 0.8～6:1.
Vulcabond is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) or hexamethylene diisocyanate (HDI) in the described step (1).
Resins, epoxy is bisphenol A type epoxy resin E51 or E44 in the described step (2).
In the described step (1)-NCO concentration monitor method be by in the Di-n-Butyl Amine method monitoring system-variation of NCO content.
Acid number is measured by the following method in the described step (2):
Sample thief (0.5～1.0g) places the Erlenmeyer flask of 250mL, and the acetone soln that adds the 20mL volume dissolves sample fully, drips 2～3 phenolphthalein indicator, with the KOH-ethanol standard solution titration of 0.1mol/L till the pink, counting;
Do blank test, the blank test method: get the acetone soln of 20mL, drip 2～3 phenolphthalein indicators, with the KOH-ethanol standard solution titration of 0.1mol/L till the pink, counting;
Acid number=56.1 * [(V-V
0) c/m]
In the formula: the KOH volume that V-the titration sample is consumed, Unit;
V
0The KOH volume that-titration blank is consumed, Unit;
M-sample mass, the g of unit;
The volumetric molar concentration of c-KOH ethanolic soln, the mol/mL of unit.
A kind of sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION is by method for preparing.
A kind of sulfonic acid type water-based of the present invention UV polyurethane modified epoxy ACRYLIC EMULSION is the preparation method can realize as follows:
(1) with HDI and HEA realization-NCO and-OH reaction, reaction obtains half affixture of half end capped containing-NCO.
(2) esterification by ring opening of Resins, epoxy and three carboxyl Phenylsulfonic acids reaction, reaction obtains epoxy three carboxyl benzene sulfonates.
With the epoxy three carboxyl benzene sulfonates that contain in the step (1)-obtain in half affixture of NCO group and the step (2) under the katalysis of 1% DBTDL with 45 ℃ of reactions.
Product in the step (3) is neutralized with triethylamine
Add water-dispersion and get sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION.
The present invention is an initial feed with Resins, epoxy, three carboxyl Phenylsulfonic acids, vulcabond and Hydroxyethyl acrylate or hydroxypropyl acrylate, through esterification by ring opening ,-NCO adds water-dispersion and obtains the finished product with-OH reaction, neutralization.
With respect to prior art, beneficial effect of the present invention is as follows:
(1) at first by the esterification by ring opening reaction of three carboxyl Phenylsulfonic acids, introduced sulfonic group.
(2) synthetic route is simple, and side reaction is less, and is pollution-free, need not in the reaction process to purify to obtain having the product of superperformance.
(3) the present invention cooperates and makes its Resins, epoxy possess hydrophilic property by introducing sulfonic acid group and carboxyl, by in half affixture-the NCO group forms with epoxy addition-OH reacts, and introduces acrylate-basedly, can carry out photocuring reaction.
(4) to compare color and luster better for the UV curable water-borne epoxy emulsion that contains sulfonic acid type and carboxylic acid type, and stability in storage is more excellent.
(5) synthetic route of the present invention is flexible, can synthesize the water-based UV cured resin of multiple functionality.
Embodiment
The present invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment expresses.
Embodiment 1
(1) under nitrogen protection, Hydroxyethyl acrylate HEA or Propylene glycol monoacrylate HPA and dibutyl tin laurate (DBTDL) are added drop-wise in the isophorone diisocyanate (IPDI), keep 40 ℃ of temperature of reaction, in the monitoring system-change in concentration of NCO, no longer change up to-NCO concentration, the mol ratio of HEA or HPA and vulcabond is 1:1; The mass ratio of dibutyl tin laurate and Hydroxyethyl acrylate or Propylene glycol monoacrylate is 0.9:100, gets half affixture of vulcabond;
(2) the esterification by ring opening reaction under the effect of catalyzer triphenyl phosphorus with Resins, epoxy E51 and three carboxyl Phenylsulfonic acids, the mol ratio of Resins, epoxy and three carboxyl Phenylsulfonic acids is 2:1, initial acid value is the 208.8mgKOH/g resin, is warming up to 150 ℃ behind 120 ℃ of reaction 2h, continues reaction 3h.When acid number was reduced to the 104.4mgKOH/g resin, stopped reaction promptly obtained epoxy three carboxyl benzene sulfonates.Acid number is measured by the following method:
Sample thief m (the m value is 0.5～1.0g) to place the Erlenmeyer flask of 250mL, and the acetone soln that adds the 20mL volume dissolves sample fully, drips 2～3 phenolphthalein indicator, with the KOH-ethanol standard solution titration of 0.1mol/L till the pink, counting; Do blank test simultaneously, the blank test method: get the acetone soln of 20mL, drip 2～3 phenolphthalein indicators, with the KOH-ethanol standard solution titration of 0.1mol/L till the pink, counting;
Acid number=56.1 * [(V-V
0) c/m]
In the formula: the KOH volume that V-the titration sample is consumed, Unit;
V
0The KOH volume that-titration blank is consumed, Unit;
M-sample mass, the g of unit;
The volumetric molar concentration of c-KOH ethanolic soln, the mol/mL of unit.
(3) with acetone solution dibutyl tin laurate (DBTDL), be added drop-wise in the mixture of half affixture that is mixed with in the step (1) and the epoxy three carboxyl benzene sulfonates in the step (2), keep 40 ℃ of temperature of reaction, 2274cm in the reaction mixture infrared spectra
-1The absorption peak completely dissolve, the mol ratio of half affixture and epoxy three carboxyl benzene sulfonates is 2:1; The mass ratio of dibutyl tin laurate and epoxy three carboxyl benzene sulfonates is 0.5:100;
(4) add triethylamine (TEA), at room temperature carry out neutralization reaction 0.5h, add water-dispersion and can obtain sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION, the mol ratio of triethylamine and three carboxyl benzene sulfonates is 2:1.
Embodiment 2
(1) under nitrogen protection, Hydroxyethyl acrylate HEA or Propylene glycol monoacrylate HPA and dibutyl tin laurate (DBTDL) are added drop-wise in the tolylene diisocyanate (TDI), keep 45 ℃ of temperature of reaction, in the monitoring system-change in concentration of NCO, no longer change up to-NCO concentration, the mol ratio of HEA or HPA and vulcabond is 1:1.05; The mass ratio of dibutyl tin laurate and Hydroxyethyl acrylate or Propylene glycol monoacrylate is 1.0:100, gets half affixture of vulcabond;
(2) the esterification by ring opening reaction under the effect of catalyzer triphenyl phosphorus with Resins, epoxy E44 and three carboxyl Phenylsulfonic acids, the mol ratio of Resins, epoxy and three carboxyl Phenylsulfonic acids is 1:2, initial acid value is the 433.6mgKOH/g resin, is warming up to 150 ℃ behind 125 ℃ of reaction 1.5h, continues reaction 3.5h.When acid number was reduced to the 325.2mgKOH/g resin, stopped reaction promptly obtained epoxy three carboxyl benzene sulfonates.The mensuration of acid number is with embodiment 1.
(3) with acetone solution dibutyl tin laurate (DBTDL), be added drop-wise in the mixture of half affixture that is mixed with in the step (1) and the epoxy three carboxyl benzene sulfonates in the step (2), keep 50 ℃ of temperature of reaction, 2274cm in the reaction mixture infrared spectra
-1The absorption peak completely dissolve, the mol ratio of half affixture and epoxy three carboxyl benzene sulfonates is 2:1; The mass ratio of dibutyl tin laurate and epoxy three carboxyl benzene sulfonates is 0.8:100.
(4) add triethylamine (TEA), at room temperature carry out neutralization reaction 1.0h, add water-dispersion and can obtain sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION, the mol ratio of triethylamine and three carboxyl benzene sulfonates is 5.7:1.
Embodiment 3
(1) under nitrogen protection, Hydroxyethyl acrylate HEA or Propylene glycol monoacrylate HPA and dibutyl tin laurate (DBTDL) are added drop-wise in the hexamethylene diisocyanate (HDI), keep 50 ℃ of temperature of reaction, in the monitoring system-change in concentration of NCO, no longer change up to-NCO concentration, the mol ratio of HEA or HPA and vulcabond is 1:1; The mass ratio of dibutyl tin laurate and Hydroxyethyl acrylate or Propylene glycol monoacrylate is 1.1:100, gets half affixture of vulcabond;
(2) the esterification by ring opening reaction under the effect of catalyzer triphenyl phosphorus with Resins, epoxy E51 and three carboxyl Phenylsulfonic acids, the mol ratio of Resins, epoxy and three carboxyl Phenylsulfonic acids is 3:1, initial acid value is the 135.68mgKOH/g resin, is warming up to 150 ℃ behind 120 ℃ of reaction 2h, continues reaction 3.5h.When acid number was reduced to the 33.92mgKOH/g resin, stopped reaction promptly obtained epoxy three carboxyl benzene sulfonates.The mensuration of acid number is with embodiment 1.
(3) with acetone solution dibutyl tin laurate (DBTDL), be added drop-wise in the mixture of half affixture that is mixed with in the step (1) and the epoxy three carboxyl benzene sulfonates in the step (2), keep 45 ℃ of temperature of reaction, 2274cm in the reaction mixture infrared spectra
-1The absorption peak completely dissolve, the mol ratio of half affixture and epoxy three carboxyl benzene sulfonates is 3:1; The mass ratio of dibutyl tin laurate and epoxy three carboxyl benzene sulfonates is 0.9:100;
(4) add triethylamine (TEA), at room temperature carry out neutralization reaction 1.0h, add water-dispersion and can obtain sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION, the mol ratio of triethylamine and three carboxyl benzene sulfonates is 0.9:1.
Embodiment 4
(1) under nitrogen protection, Hydroxyethyl acrylate HEA or Propylene glycol monoacrylate HPA and dibutyl tin laurate (DBTDL) are added drop-wise in the tolylene diisocyanate (TDI), keep 50 ℃ of temperature of reaction, in the monitoring system-change in concentration of NCO, no longer change up to-NCO concentration, the mol ratio of HEA or HPA and vulcabond is 1:1.05; The mass ratio of dibutyl tin laurate and Hydroxyethyl acrylate or Propylene glycol monoacrylate is 1.0:100, gets half affixture of vulcabond;
(2) the esterification by ring opening reaction under the effect of catalyzer triphenyl phosphorus with Resins, epoxy E51 and three carboxyl Phenylsulfonic acids, the mol ratio of Resins, epoxy and three carboxyl Phenylsulfonic acids is 1:1, initial acid value is the 382.8mgKOH/g resin, is warming up to 150 ℃ behind 130 ℃ of reaction 1h, continues reaction 3h.When acid number was reduced to the 191.4mgKOH/g resin, stopped reaction promptly obtained epoxy three carboxyl benzene sulfonates.The mensuration of acid number is with embodiment 1.
(3) with acetone solution dibutyl tin laurate (DBTDL), be added drop-wise in the mixture of half affixture that is mixed with in the step (1) and the epoxy three carboxyl benzene sulfonates in the step (2), keep 50 ℃ of temperature of reaction, 2274cm in the reaction mixture infrared spectra
-1The absorption peak completely dissolve, the mol ratio of half affixture and epoxy three carboxyl benzene sulfonates is 1:1; The mass ratio of dibutyl tin laurate and epoxy three carboxyl benzene sulfonates is 1.0:100;
(4) add triethylamine (TEA), at room temperature carry out neutralization reaction 0.9h, add water-dispersion and can obtain sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION, the mol ratio of triethylamine and three carboxyl benzene sulfonates is 2.4:1.
The comparative illustration of embodiment product performance and prior art
In the prior art, utilize with the preparation of cis-butenedioic anhydride as hydrophilic monomer modified isocyanate grafting epoxy acrylic resin self-emulsifying system.Its concrete preparation technology is: at first with isocyanic ester and HEA with etc. molar ratio reaction make half affixture; Again in the four-hole boiling flask that thermometer, prolong, dropping funnel are housed, add 50g Resins, epoxy E51, be warming up to 80 ℃, drip the vinylformic acid 9.2g that is dissolved with hydroquinone of polymerization retarder and catalyst of triethylamine for the 1:1 equivalent in molar ratio, measuring initial acid value is the 121mgKOH/g resin, slowly is warming up to 110 ℃ of reaction 5h then to acid number＜5mgKOH/g resin stopped reaction.With half affixture and epoxy acrylate with etc. the amount of mol ratio mix, be warming up to 60 ℃, react 2270cm to the Infrared Spectra of Mixture
-1Absorption peak disappears substantially, and reaction finishes, and adds the 12.5g cis-butenedioic anhydride and is warming up to 80 ℃ of reaction 90min, adds in the 12.9g triethylamine 100% again and 1h, adds water-dispersion and promptly obtains target product.
The concrete preparation technology's products obtained therefrom of prior art with the preceding paragraph is made the contrast sample, and is as shown in table 1 with the emulsion property index contrast of various embodiments of the present invention."〉72h in the chemical resistance in the table 1 " time that is meant is greater than 72 hours, but in 82 hours; "〉48h " time that is meant is greater than 48 hours, but in 58 hours.Explanation hereby.By table 1 as seen, all there are gap in contrast sample gained emulsion and film performance and products obtained therefrom of the present invention, curing speed is longer 8 hours than the embodiment of the invention, and in the chemical resistance, short 24 hours of alkaline-resisting (5%NaOH) and salt resistant character (5%NaCl) test period.
Each embodiment of table 1 obtains emulsion property
Claims (4)
1. the preparation method of sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION is characterized in that comprising following steps:
(1) under nitrogen protection, Hydroxyethyl acrylate or Propylene glycol monoacrylate and dibutyl tin laurate are added drop-wise in the vulcabond, keep 40～50 ℃ of temperature of reaction, in the monitoring system-change in concentration of NCO, no longer change up to-NCO concentration, half affixture of vulcabond; The mol ratio of Hydroxyethyl acrylate or Propylene glycol monoacrylate and vulcabond is 1:1～1.05; The mass ratio of dibutyl tin laurate and Hydroxyethyl acrylate or Propylene glycol monoacrylate is 0.9～1.1:100;
(2) with mol ratio be Resins, epoxy and the esterification by ring opening reaction under the effect of catalyzer triphenyl phosphorus of three carboxyl Phenylsulfonic acids of 3:1～1:2, at 120～150 ℃ of reaction 3～5h, acid number is reduced to 25 of system initial acid value～75% o'clock stopped reaction, and reaction obtains epoxy three carboxyl benzene sulfonates;
(3) use the acetone solution dibutyl tin laurate, be added drop-wise in the mixture of half affixture that is mixed with the vulcabond in the step (1) and the epoxy three carboxyl benzene sulfonates in the step (2), keep 40～50 ℃ of temperature of reaction, 2274cm in the reaction mixture infrared spectra
-1The absorption peak completely dissolve, the mol ratio of half affixture of vulcabond and epoxy three carboxyl benzene sulfonates is 1:1～3:1; The mass ratio of dibutyl tin laurate and epoxy three carboxyl benzene sulfonates is 0.5～1.0:100;
(4) add triethylamine, at room temperature carry out neutralization reaction 0.5～1.0h, add water-dispersion and can obtain sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION, the mol ratio of triethylamine and three carboxyl benzene sulfonates is 0.8～6:1;
Vulcabond is isophorone diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate in the described step (1);
Resins, epoxy is bisphenol A type epoxy resin E51 or E44 in the described step (2).
2. the preparation method of sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION according to claim 1 is characterized in that: in the described step (1)-NCO concentration monitor method be by in the Di-n-Butyl Amine method monitoring system-variation of NCO content.
3. the preparation method of sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION according to claim 1 is characterized in that: acid number is measured by the following method in the described step (2):
Get the Erlenmeyer flask that synthetic resins 0.5～1.0g places 250mL, the acetone soln that adds the 20mL volume dissolves sample fully, drips 2～3 phenolphthalein indicator, with the KOH-ethanol standard solution titration of 0.1mol/L till the pink, counting;
Do blank test, the blank test method: get the acetone soln of 20mL, drip 2～3 phenolphthalein indicators, with the KOH-ethanol standard solution titration of 0.1mol/L till the pink, counting;
Acid number=56.1 * [(V-V0) c/m]
In the formula: the KOH volume that V-the titration sample is consumed, Unit;
V
0The KOH volume that-titration blank is consumed, Unit;
M-sample mass, the g of unit;
The volumetric molar concentration of c-KOH ethanolic soln, the mol/mL of unit.
4. sulfonic acid type water-based UV polyurethane modified epoxy ACRYLIC EMULSION is characterized in that each described method preparation by claim 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110251751 CN102432795B (en) | 2011-08-30 | 2011-08-30 | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110251751 CN102432795B (en) | 2011-08-30 | 2011-08-30 | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432795A CN102432795A (en) | 2012-05-02 |
| CN102432795B true CN102432795B (en) | 2013-07-24 |
Family
ID=45981173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110251751 Expired - Fee Related CN102432795B (en) | 2011-08-30 | 2011-08-30 | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432795B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633984B (en) * | 2012-04-06 | 2013-12-25 | 长兴（广州）电子材料有限公司 | Polyurethane-acrylate oligomer, and synthesis method and application thereof |
| CN103554418B (en) * | 2013-11-22 | 2015-07-01 | 珠海长先新材料科技股份有限公司 | Method for preparing photosensitive resin for solder mask ink |
| CN103821028B (en) * | 2014-03-03 | 2018-04-17 | 江门职业技术学院 | High-performance water-based UV cured gloss oil for paper and preparation method thereof |
| CN104788626B (en) * | 2015-03-31 | 2017-06-23 | 中科院广州化学有限公司 | A kind of hydro-thermal responsive type modified epoxy acrylic ester and its preparation method and application |
| CN109608611A (en) * | 2018-10-23 | 2019-04-12 | 合肥科天水性科技有限责任公司 | A kind of epoxy acrylic resin modified aqueous polyurethane and preparation method thereof |
| CN113801565B (en) * | 2021-09-29 | 2022-11-04 | 长兴（广州）光电材料有限公司 | UV-cured water-based cathode electrophoretic coating and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178952A (en) * | 1989-03-30 | 1993-01-12 | Toyo Boseki Kabushiki Kaisha | Radiation curable resin, composition thereof and precoated metal made therefrom |
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| CN1746204A (en) * | 2005-09-10 | 2006-03-15 | 江南大学 | Water photosensitive resin emulsion and preparation thereof |
| EP1306399B1 (en) * | 2001-10-26 | 2007-03-28 | Kansai Paint Co., Ltd. | Photocurable primer composition and coating method by use of the same |
| CN101397363A (en) * | 2008-08-19 | 2009-04-01 | 东莞市佳景印刷材料有限公司 | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof |
| CN101481451A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
| CN101921373A (en) * | 2010-08-17 | 2010-12-22 | 华南理工大学 | Acrylic modified epoxy resin emulsion and preparation method thereof |
-
2011
- 2011-08-30 CN CN 201110251751 patent/CN102432795B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178952A (en) * | 1989-03-30 | 1993-01-12 | Toyo Boseki Kabushiki Kaisha | Radiation curable resin, composition thereof and precoated metal made therefrom |
| EP1306399B1 (en) * | 2001-10-26 | 2007-03-28 | Kansai Paint Co., Ltd. | Photocurable primer composition and coating method by use of the same |
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| CN1746204A (en) * | 2005-09-10 | 2006-03-15 | 江南大学 | Water photosensitive resin emulsion and preparation thereof |
| CN101397363A (en) * | 2008-08-19 | 2009-04-01 | 东莞市佳景印刷材料有限公司 | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof |
| CN101481451A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
| CN101921373A (en) * | 2010-08-17 | 2010-12-22 | 华南理工大学 | Acrylic modified epoxy resin emulsion and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘刚.紫外光固化聚丙烯酸酯涂料的研究.《化学世界》.1997,(第04期), |
| 王萃萃等.紫外光固化水性聚氨酯丙烯酸酯的研究进展.《聚氨酯》.2009,(第08期), |
| 紫外光固化水性聚氨酯丙烯酸酯的研究进展;王萃萃等;《聚氨酯》;20090815(第08期);全文 * |
| 紫外光固化聚丙烯酸酯涂料的研究;刘刚;《化学世界》;19970425(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432795A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432795B (en) | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method | |
| CN102993404B (en) | Photosensitive fluorosilicone segmented urethane acrylate oligomer and preparation method thereof | |
| CN107793544B (en) | A kind of environment-friendly polyurethane curing agent and its preparation method and application | |
| CN102344539B (en) | Silicon-containing double-curing group resin and preparation method thereof | |
| CN106866929A (en) | A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application | |
| CN101397363B (en) | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof | |
| CN105175641A (en) | Silane coupling agent modified polyurethane-acrylate composite emulsion and preparation method thereof | |
| CN101659809A (en) | Water-based UV black ink with super-high solid content and preparation method thereof | |
| CN103833956A (en) | High molecular weight urethane acrylate resin and preparation method thereof | |
| CN106750140A (en) | A kind of amine modified urethane acrylate light-cured resin and preparation method thereof | |
| CN102863829A (en) | Humidity and ultraviolet dual-cured polyurethane woodware coating and preparation method thereof | |
| CN104031231A (en) | Ultraviolet-curing waterborne epoxy-polyurethane-acrylate copolymer resin anticorrosive coating and preparation method thereof | |
| CN101274977B (en) | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof | |
| CN102199271A (en) | Adiation-hardenable polyurethane resin and preparation method thereof | |
| CN104693994A (en) | Ultraviolet photocuring coating containing inorganic pigment and filler and preparation method thereof | |
| CN107189032A (en) | A kind of multifunctional UV solidification polyurethane vegetable oil acid esters prepolymers and its preparation method and application | |
| CN105175679A (en) | Waterborne polyurethane emulsion modified by epoxy resin and preparation method thereof | |
| CN108587271A (en) | A kind of aqueous UV polyurethane coatings and preparation method thereof | |
| CN104448235A (en) | Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin | |
| CN106752880A (en) | A kind of glossy leather finishing agent of ultraviolet light solidfication water polyurethane acrylate | |
| CN102101967A (en) | Single component polyurea polyurethane coating and preparation method thereof | |
| CN110615861B (en) | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof | |
| CN102977335A (en) | Method for preparing resin containing light-heat dual cured groups from epoxy chloropropane as raw material | |
| CN103626956A (en) | Modified polyisocyanate, water dispersible crosslinking agent and preparation method thereof | |
| CN101544741B (en) | Method for preparing dianion type water-based light-cured polyurethane resin through chain extending method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130724 Termination date: 20200830 |